Sialic Acids

Rapid progress in the field of sialic acids has made it desirable to collect the new data about these unique sugars and to continue the series of books on this topic. In 1960, A. GOTTSCHALK wrote "The Chemistry and Biology of Sialic Acids and Related Substances" (Cambridge University Press) and in 1976, A. ROSENBERG and C. -L. SCHENGRUND published "Biological Roles of Sialic Acids" (Plenum Press). In this book emphasis is given to various modern methods used in the isolation and analysis of sialic acids. New approaches to the synthesis of free and bound sialic acids are described and the vast field of occurrence and metabolism of these substances is reviewed. Sialidoses are dealt with in one of the chapters, because sialidases have been recognized as factors of pathophysiological im­ portance. As knowledge is increasing about the involvement of sialic acids in many aspects of cell biology, another chapter is devoted to these phenomena. With this book I intend to demonstrate modern trends in sialic acid chemistry and biochemistry, and I hope that it will be of practical use and find its place in laboratories rather than in libraries. This publication offers an opportunity to thank all colleagues in many countries, including my coworkers at the universities of Bochum and Kiel, for their cooperation, stimulating discussions and, very important, useful criticism. The continuous cooperation with J. F. G. VLIEGENTHART and his coworkers, Utrecht, has been rewarding in many respects.

Inhalt

A. Introduction.- B. Occurrence of Sialic Acids.- I. Introduction.- II. Viruses.- III. Bacteria.- IV. Fungi, Algae, and Plants.- V.Protozoa.- VI. Porifera, Platyhelminthes, Nemertinea, Ctenophora, andCoelenterata.- VII. Sipuncula, Annelida, Arthropoda, and Mollusca.- VIII. Bryozoa, Brachiopoda, Chaetognatha, and Echinodermata.- IX. Hemichordata, Urochordata, and Cephalochordata.- X.Vertebrata.- 1. Pisces 13.- 2. Amphibia.- 3. Reptilia.- 4. Aves.- 5. Mammalia.- a) Introduction.- b) Oligosaccharides.- ?) Milk and Colostrum.- ?) Urine.- ?) Nucleotide Sugars.- c) Glycoproteins.- ?) Serum.- ?) Epithelial or Mucus Glycoproteins.- ?) Membrane Glycoproteins.- ?) Brain Glycoproteins.- ?) Milk, Colostrum and Urine Glycoproteins and Glycopeptides.- ?) Hormone and Enzyme Glycoproteins.- ?) Lipoproteins.- ?) Miscellaneous.- d) Gangliosides.- XI. The Nature of Sialic Acids.- 1. Introduction.- 2. Free Sialic Acids.- 3. Glycosidically Linked Sialic Acids.- a) The Type of Sialic Acid.- b) Sialyloligosaccharide Structural Considerations.- ?) Terminal Linear Position.- ?) Terminal "Side-Chain Position".- ?) Internal Sialic Acids in OUgosialylglycoconjugates and Sialylpoly- saccharides.- ?) Internal Sialic Acids in the Echinodermata.- XII. Evolution of the Sialic Acids.- Biblography.- C. Isolation and Purification of Sialic Acids.- I. Introduction.- II. Acid Hydrolysis.- III. Enzymic Hydrolysis.- IV. Lipid Extraction.- V. Ion-Exchange Chromatography.- VI. Cellulose Chromatography.- VII. Crystallization.- VIII. Other Methods.- D. Synthesis of Sialic Acids and Sialic Acid Derivatives.- I.Introduction.- II. Glycosides of Sialic Acids.- III. Sialodisaccharides.- IV. 2-Deoxy-2,3-dehydro-N-acylneuraminic Acids.- V. Methylated Sialic Acids.- VI. Isotopically Labelled Sialic Acids.- VII. Substrates for Sialidase Investigations.- VIII. C7- and C8-Analogues of Sialic Acids.- IX. Miscellaneous Sialic Acids and Sialic Acid Derivatives.- E. Colorimetry and Thin-Layer Chromatography of Sialic Acids.- I. Introduction.- II. Colorimetry and Fluorimetry.- 1. Diphenol Reagent Assays.- a) Orcinol.- b) Resorcinol.- ?) Resorcinol/Cu2+ Assay.- ?) Periodate/Resorcinol/Cu2+ Assay.- 2. Periodic Acid/Thiobarbituric Acid Assays.- a) The Warren and Aminoff Methods.- b) Interference.- 3. Periodic Acid/Methyl-3-Benzothiazolinone-2-Hydrazone Method.- 4. Fluorimetrie Assays.- 5. Enzymic Assays.- 6. O-Acyl Group Assay.- 7. Automatic Procedures.- 8. High Performance Liquid Chromatography.- 9. Other Methods.- 10. Quantitative Problems in Sialic Acid Release.- III. Thin-Layer Chromatography.- 1. Chromatographic Systems.- 2. Visualization.- 3. Two-Dimensional Techniques.- a) Individual Sialic Acid Determination.- b) 0-Acyl Group Identification.- c) Sialic Acid Identification in Oligosaccharides.- 4. Paper Chromatography.- F. Gas-Liquid Chromatography and Mass Spectrometry of Sialic Acids.- I. Introduction.- II. Gas-Liquid Chromatography.- 1. Quantitative Sugar Analysis, Including Sialic Acid.- 2. Hydrolytic Release of Sialic Acids from Sialobiopolymers.- 3. Preparation and Analysis of Trimethylsilylated N,0-AcyNeuraminic Acid Methyl Esters.- 4. Preparation and Analysis of Pertrimethylsilylated N,0-Acylneuraminic Acids.- 5. Analysis of Acetyl and/or Glycolyl Residues of Sialic Acid.- III. Gas-Liquid Chromatography/Mass Spectrometry.- 1. Mass Spectrometric Identification Procedure.- 2. Analysis of (0-Acylated) N-Acylneuraminic Acids Isolated from Biological Material.- 3. Sialic Acids and Methylation Analysis.- 4. Miscellaneous Sialic Acids and Sialic Acid Derivatives.- 5. Quantitative Analysis of Sialic Acids by g.l.c./m.s.- 6. Sialooligosaccharides, Sialoglycolipids, and Sialoglycopeptides.- G. NMR Spectroscopy of Sialic Acids.- I. Introduction.- II. 1H-NMR Spectroscopy.- 1. N-Acetyl- and N-Glycolylneuraminic Acid.- 2. O-Acetylated Neuraminic Acid Derivatives.- 3. Analysis of Sialic Acid Linkage Types in Glycoconjugates.- a) The Anomeric Configuration of Sialic Acid.- b) Sialic Acid in Carbohydrate Chains of the N-Acetyllactosamine Type.- c) Sialic Acid in 0-Glycosidically Linked Carbohydrate Chains.- d) CMP-N-Acetylneuraminic Acid and Degradation Products.- 4. Enzymic and Chemical Conversions.- 5. Complexes of Sialic Acids with Ca2+.- III. 13C-NMR Spectroscopy.- 1. N-Acetyl- and Glycolylneuraminic Acid.- 2. O-Acetylated Neuraminic Acid Derivatives.- 3. Polysaccharides.- 4. Esterified Polysaccharides.- 5. CMP-N-Acetylneuraminic Acid and 2-Deoxy-2,3-dehydro-N-acetylneuraminic Acid.- 6. Complexes of Sialic Acids with Ca2+.- 7. 13C-Relaxation Studies on Sialic Acids and Sialyllactoses.- IV. Analytical Procedures.- 1. Instrumentation.- 2. Solutions.- H. Histochemistry of Sialic Acids.- I. Introduction.- II. Histochemical Identification of Sialic Acids.- 1. General.- 2. Methods Based upon Staining with Cationic Dyes.- a) Staining at Different pH's.- b) Removal of Specific Components Contributing to the Staining.- ?) Use of Enzymatic Procedures.- ?) Use of Chemical Procedures.- i) Acid Hydrolysis.- ii) Methylation.- c) Inhibition of Staining with Alcian Blue in the Presence of Varying Concentrations of Inorganic Salts (C.E.C. Methods).- 3. Methods Based upon the Use of Periodate Oxidation.- a) The PAS Reaction.- b) The Periodic Acid/Phenylhydrazine/Schiff (PAPS) Procedure.- c) The Use of Very Dilute Periodic Acid.- d) Identification of Side Chain O-Acylated Sialic Acid.- ?) PBT/KOH/PAS Technique.- ?) PAT/KOH/PAS Procedure.- ?) 9-0-Acyl Sialic Acids.- 4. Methods Based upon the Use of Lectins.- III. Staining and Control Procedures.- 1. Fixation and Processing.- 2. PAS Technique.- 3. PBT/KOH/PAS Technique.- 4. PAT/KOH/PAS Technique.- 5. High Iron Diamine/Alcian Blue Method.- 6. Alcian Blue (pH 2.5).- 7. Alcian Blue (pH 1.0).- 8. Neuraminidase Digestion.- 9. Acid Hydrolysis.- BibHography.- I. Metabolism of Sialic Acids.- I. Introduction.- II. De novo Biosynthesis of Sialic Acids.- 1. Introduction.- 2. From Glucose to UDP-N-Acetylhexosamine.- 3. Formation of NeuSAc.- 4. Activation and Modification of Neu5Ac.- III. Sialyltransfer.- 1. Introduction.- 2. Sialyltransfer in Cells and Cell-Free Systems: Cellular Location.- a) Intact Cells.- ?) N-Glycosidically Linked Oligosaccharide Chains.- ?) O-Glycosidically Linked Oligosaccharides (Ser/Thr-GalNAc Type).- ?) Glycolipids (Gangliosides).- ?) Membrane Glycoconjugates.- b) Cell-Free Systems.- ?) N-Glycosidically Linked Oligosaccharide Chains.- ?) O-Glycosidically Linked Oligosaccha…